Reduction-Oxidation Reactions 3.

1 - REDOX in Outline

Jorge Ramos, Ph.D.

Electron transfer reactions are collectively known as reduction-oxidation or REDOX reaction. No substance is ever oxidized unless something else is reduced. Otherwise,
electrons would appear as a product of the reaction, which is never observed. An electron accepting substance is called the oxidizing agent because it helps something else to be oxidized. The substance that supplies the electrons is called the reducing agent because it helps something else to be reduced. An easy way to remember which element is being oxidized or reduced is by placing the numbers in a number line < (-)-(-4)-(-3)-(-2)-(-1)-0-(+1)-(+2)-(+3)-(+4)-(+) > The word reduction has the meaning you would expect from the number line. The word means reducing the value or moving towards the negative side of the number line. Example 3.1a Identify the element that is reduced and the element that is oxidized during the formation of Magnesium Oxide. Recall that elements in their pure form have a 0 (zero) oxidation state.

2Mg + O2 2MgO Mg0 Mg2+ + 2eO2 + 4e- O2First we write the half reactions:

Oxygen goes from 0 to 2-. Thus it moved towards the negative side of the number line and then the element that was REDUCED. Since electrons are negative, adding electrons makes the oxidation number smaller. Magnesium moves from 0 to 2+. Thus it moved towards the positive side of the number line and was OXIDIZED. Since electrons are negative, removing electrons makes the oxidation number larger. Thus we now know that the oxidation numbers behave just like simple arithmetic. If you add a minus one (1-) to a number it will become smaller, if you add an electron (e-) to an element its oxidation number will become smaller. There are six main rules for assigning oxidation numbers. The order in which these rules are written is very important because if two of them contradict each other then the last one listed takes precedence. Rule 1. All pure substances have an oxidation number of zero. This applies to any
pure substance whether it is a diatomic gas like O2 or a piece of pure metal like Iron (Fe). Examples of

their position in a particular group have that same oxidation number. An example is Cl which is usually in the form Cl- in compounds; this will have an oxidation number of -1 in compounds.

Rule 2. In compounds, elements that usually have an ionic charge imparted by

Reduction-Oxidation Reactions

Jorge Ramos, Ph.D.

Rule 3. When two or more usually negatively charged ions are involved in a

compound, the one with the highest electronegativity value is given its ionic charge as the oxidation number; the others are worked out normally. An example is OF2. F is more electronegative, and so it is assigned the value of -1.

Rule 4. Oxygen in a compound always has an oxidation number of -2 Rule 5. Hydrogen in compounds always has an oxidation number of +1 except in
the rare case of Metal Hydrides where it has a value of -1.

overall charge of that compound or molecule. For example CO2 has no overall charge and so the oxidation numbers must tally to zero. The sulfate ion, SO42-, has an overall charge of -2, so the oxidation numbers must tally to -2.

Rule 6. The oxidation numbers in the compound or molecule must total to the

Example 3.1b Find the oxidation numbers in the elements from CH2Cl2 Rule 2: Cl has on oxidation number of -1 Rule 5: Hydrogen has an oxidation number of +1. This is not a metal hydride so the exception does not apply. Rule 6: The sum of oxidation numbers must add up to the charge of the molecule

C X X X

+ + = =

2Cl- + 2H+ = 0 (2-) + (2+) = 0 0 + (+2) + (-2) 0

Thus the oxidation number of Carbon in CH2Cl2 is 0. Example 3.1c Find the oxidation numbers in the elements from H2O2 Rule 4: Oxygen in a compound always have an oxidation number of -2 Rule 5: Hydrogen has an oxidation number of +1. This is not a metal hydride so the exception does not apply. The two rules contradict each other because if we use +1 for hydrogen and -2 for oxygen we get: 2H+ + 2O-2 = -2 Thus we eliminate rule number 4 and keep rule number 5 (Hydrogen is +1). Add rule number 6 (all oxidation numbers add up to the molecules charge) 2H+ + 2O-x = 0 2 + 2X = 0 2X = 0 - 2 X = -1 Thus the oxidation number of oxygen in H2O2 is -1.

Reduction-Oxidation Reactions 3.2 Balancing REDOX equations (Ion-Electron method)

Jorge Ramos, Ph.D.

In the Ion-Electron method, the reaction is divided into half reactions. For the reaction of Fe3+ and Sn2+ we have, Fe3+ + Sn2+ Fe2+ + Sn4+ First we write the half reactions: the oxidation of Tin and the reduction of iron, Sn2+ Sn4+ Fe3+ Fe2+ Next, we balance the atoms and the charge. For this reaction, the atoms are balanced (one tin on both sides and one iron on both sides) Sn2+ Sn4+ + 2eFe3+ + e- Fe2+ Now we balance the combined equations so that the number of electrons gained in the reduction reaction is the same as the number of electrons lost in the oxidation reaction. Sn2+ Sn4+ + 2e(Fe3+ + e- Fe2+) X 2 Because each tin looses two electrons and each iron gains one electron, the iron reduction is multiplied by 2. The combined reactions yield the final balanced equation, 2Fe3+ + 2e- + Sn2+ 2Fe2+ + Sn4+ + 2e2Fe3+ + Sn2+ 2Fe2+ + Sn4+ The previous REDOX looks so simple that it makes one wonder why we even bother going through all those steps. The answer is that not all reactions are so simple and most of the time it is necessary to through all those steps to balance a REDOX. Half-Reactions Outline: Reductant Products + e Loss of electrons (Oxidation Number increases) Oxidant + e Products Gain of electrons (Oxidation Number decreases)

Reduction-Oxidation Reactions Example 3.2a Balance the redox reaction between Gold 3+ and the Iodide ion. Au3+(aq) + I(aq) Au(s) + I2(s) The balanced half-reactions are: 2I-(aq) I2(s) + 2eAu3+(aq) + 3e Au(s) Make electrons gained equal to electrons lost: 3( 2I-(aq) I2(s) + 2e- ) 2( Au3+(aq) + 3e Au(s) ) Add the half-reactions: 2Au3+(aq) + 6e + 6I-(aq) 3I2(s) + 6e- + 2Au(s) Cancel anything that is the same on both sides: 2Au3+(aq) + 6I-(aq) 3I2(s) + 2Au(s)

Jorge Ramos, Ph.D.

Example 3.2b Balance the following redox reaction. SnCl3-(aq) + HgCl2(aq) SnCl62-(aq) + Hg2Cl2(s) The balanced half-reactions are: SnCl3-(aq) + 3Cl- SnCl62- + 2e2HgCl2 + 2e Hg2Cl2 + 2ClMake electrons gained equal to electrons lost: SnCl3-(aq) + 3Cl- SnCl62- + 2eHgCl2 + 2e Hg2Cl2 + 2ClElectrons are balanced Add the half-reactions: SnCl3-(aq) + 3Cl- + 2HgCl2 + 2e SnCl62- + 2e- + Hg2Cl2 + 2ClCancel anything that is the same on both sides: SnCl3-(aq) + Cl- + 2HgCl2 SnCl62- + Hg2Cl2

Reduction-Oxidation Reactions 3.3 Ion-Electron method for reactions involving OH- and H+.

Jorge Ramos, Ph.D.

Redox reactions are commonly run in acidic solution, in which case the reaction equations often include H2O(l), OH-(aq) and H+(aq) but you might not know whether the H2O(l) ), OH-(aq) and H+(aq) are reactants or products. For example, you may know that dichromate ions, Cr2O72-, react with nitrous acid molecules, HNO2, in acidic conditions to form chromium ions, Cr3+, and nitrate ions, NO3-. Because the reaction requires acidic conditions, you assume that H2O(l) and H+(aq) participate in some way, but you do not know whether they are reactants or products, and you do not know the coefficients for the reactants and products. An unbalanced equation for this reaction might be written Cr2O72-(aq) + HNO2(aq) Cr3+(aq) + NO3-(aq) (acidic solution)

In order to balance equations of this type, we need to add more steps to the ion-electron method. Note we have added steps 2, 3, and 4. Ion-Electron method Outline [1] Divide equation into half-reaction [2] Balance atoms other than H and O [3] Balance O by adding H2O [4] Balance H by adding H+ [5] Balance net charge by adding e[6] Make e- gain equal to e- loss and add half reactions [7] Add half reactions and cancel anything that is the same on both sides For Basic solution add steps [8] Add to both sides of the equation the same number of OH- as there are H+. [9] Combine OH- and H+ to form H2O. [10] Cancel any H2O that you can.

Example 3.3a Balance the following redox equation using the half-reaction method in acidic solution. Cr2O72-(aq) + HNO2(aq) --> Cr3+(aq) + NO3-(aq) Separate the two half reactions: Cr2O72- Cr3+ HNO2 NO3Balance atoms other than H and O Cr2O72- 2Cr3+ HNO2 NO3-

Reduction-Oxidation Reactions Add water to balance O Cr2O72- 2Cr3+ + 7H2O HNO2 + H2O NO3Add H+ to balance H: Cr2O72- + 14H+ 2Cr3+ + 7H2O HNO2 + H2O NO3- + 3H+

Jorge Ramos, Ph.D.

Balance net charge by adding e6e- + Cr2O72- + 14H+ 2Cr3+ + 7H2O HNO2 + H2O NO3- + 3H+ + 2eMake e- gain equal to e- loss and add half reactions 6e- + Cr2O72- + 14H+ 2Cr3+ + 7H2O 3(HNO2 + H2O NO3- + 3H+ + 2e-) 6e- + Cr2O72- + 14H+ 2Cr3+ + 7H2O 3HNO2 + 3H2O 3NO3- + 9H+ + 6eAdd half reactions and cancel anything that is the same on both sides 6e- + Cr2O72- + 14H+ + 3HNO2 + 3H2O 2Cr3+ + 7H2O + 3NO3- + 9H+ + 6e3 H2O in the second half-reaction cancel three of the 7 H2O in the first half-reaction 9 H+ on the right of the second half-reaction cancel nine of the 14 H+ on the left of the first half-reaction Cr2O72- + 5H+ + 3HNO2 2Cr3+ + 4H2O + 3NO3Check to make sure that the atoms and the charge are balanced. The atoms in this example balance and the sum of the charges is +3 on each side, so the equation is correctly balanced.

Example 3.3b Balance the redox reaction between MnO4- and I- in acidic then basic. . MnO4- + I- I2 + Mn2+ Separate the two half reactions: I- I2 MnO4- Mn2+

Reduction-Oxidation Reactions Balance the iodine atoms: 2I- I2

Jorge Ramos, Ph.D.

The Mn in the permanganate reaction is already balanced, so let's balance the oxygen: MnO4- Mn2++ 4H2O Add H+ to balance the 4 waters molecules: MnO4- + 8 H+ Mn2++ 4H2O Next, balance the charges in each half-reaction so that the reduction half-reaction consumes the same number of electrons as the oxidation half-reaction supplies. This is accomplished by adding electrons to the reactions: 2 I- I2 + 2e5 e- + 8 H+ + MnO4- Mn2+ + 4H2O Now multiple the oxidations numbers so that the two half-reactions will have the same number of electrons and can cancel each other out: 5(2I- I2 +2e-) 2(5e- + 8H+ + MnO4- Mn2+ + 4H2O) Now add the two half-reactions: 10 I- 5I2 + 10 e16 H+ + 2MnO4- + 10 e- 2Mn2+ + 8H2O This yields the following final equation: 10 I- + 10 e- + 16 H+ + 2 MnO4- 5 I2 + 2Mn2+ + 10 e- + 8H2O Get the overall equation by canceling out the electrons and H2O, H+, and OH- that may appear on both sides of the equation: 10I- + 16H+ + 2MnO4- 5I2 + 2Mn2+ + 8H2O For the reaction in basic solution, Add 16OH- on both sides 16OH- + 10I- + 16H+ + 2MnO4- 5I2 + 2Mn2+ + 8H2O + 16OHCombine 16OH- and 16H+ to form 16H2O 16H2O + 10I- + 2MnO4- 5I2 + 2Mn2+ + 8H2O + 16OHCancel any H2O that you can 8H2O + 10I- + 2MnO4- 5I2 + 2Mn2+ + 16OH-